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By G. H. Gronhovd, W. H. Oppelt

Complete gasification to produce synthesis gas for manufacture of synthetic chemicals and fuels offers possibilities for utilization of the vast lignite fuel deposits in the U.S. The design of a slugging, fixed-bed, pressure gasification pilot Plant is described. Results are presented for initial operation of the plant at moderate pressure and using low-temperature char as fuel. Gasification of solid fuels is becoming increasingly important in the future overall energy picture, both in this country and abroad. Snythesis gas from gasification of coal consists chiefly of carbon monoxide and hydrogen, and after suitable purification and modification this gas can be used in the production of synthetic ammonia, methanol, higher alcohols, and synthetic liquid fuels, or as a reducing gas in the metallurgical field.' Most synthesis gas used in this country is made from natural gas, petroleum oils, and refining tail-gases, but the direct gasification of coal will become more attractive as costs of petroleum oils and natural gas increase.' A gasification process designed for use with brown coal and lignite was developed by the German Lurgi Co. prior to World War 11. In this process a fixed bed of lump-sized fuel is gasified with steam and oxygen at pressures ranging from 370 to 440 psi. Effective heat exchange between the ascending high-temperature gases and the descending solid fuel results in low gas outlet temperatures, high thermal efficiency, and favorable oxygen consumption. Lurgi gasifiers are used commercially for the production of synthesis gas or as a substitute for coal gas in many countries, including Germany, Czechslovakia, Great Britain, South Africa, Australia and Pakistan.3-6 The chief disadvantage of the conventional Lurgi gasifier which operates under nonclinkering conditions is that large quantities of excess steam must be supplied with the oxygen-steam mixture to reduce the temperature in the fuel bed below fusion temperature of the ash. Most of the steam leaves the gasifier undecomposed with the product gas and, after cooling, produces large amounts of dilute liquor. Evaluation of fixed-bed gasification experiments using dry-ash removal indicated that by increasing the oxygen concentration in the oxygen-steam blast the temperature in the combustion zone could be raised high enough to operate under slagging conditions. 7-8 Operation of a fixed-bed pressure gasifier under slagging conditions would reduce the steam requirements and the volume of waste liquor and would increase the steam decomposition, the overall thermal efficiency of the process, and the rate of gas production per unit cross sectional area of the gasifier. Because the Lurgi gasification process, modified for slagging operation, offered possibilities for efficient gasification of American lignite, the Bureau of Mines decided to investigate the process on a pilot-plant scale at the Grand Forks, N. D., Lignite Research Laboratory. DESIGN Description of Pilot Plant: A flowsheet of the Grand Forks slagging gasification pilot plant is presented in Fig. 1. The gasifier unit consits of the coal lock, the gas generator, and the slag lock. The fuel, which is periodically charged to the coal lock, moves by gravity flow into the generator and is continuously gasified by an oxygen-steam mixture introduced at the bottom of the gasifier. Molten slag is formed at the hearth and flows through a central taphole into a water quench bath. The slag-water slurry is periodically discharged from the slag lock. Process steam is generated and superheated in separately-fired, oil-burning units. Oxygen is supplied to the gasifier from a gas storage bank located some distance from the pilot plant. The capacity of the oxygen storage bank is about 130,000 standard cu ft at 2200 psig. Liquid oxygen is delivered by truck and is converted to gas during the filling operation. The superheated steam and oxygen are metered separately, then mixed and fed to the gasifier tuyeres. The gas generator is surrounded by a water jacket. The steam formed is separated in the steam drum and then discharged to the gas offtake, thus equaliz-

Jan 1, 1961

By C. R. Ramachandra, C. C. Patel

Flotation of chalcopyrite from a low grade ore was studied by using different xanthates and dixanthogens as collectors and by conditioning the flotation pulp with oxidizing gaseous systems. The improvement in the recovery of chalcopyrite with the oxidizing systems was mainly due to the auto-activation of chalcopyrite, leading to the enhanced adsorption of xanthates and dixanthogens even when the latter were formed by oxidation of the xanthates. With air or oxygen as oxidizing system, the amount of ethyl xanthate required at pH 8.5 was much less than normally employed in the industry, the recovery being 97-99% of chalcopyrite with a concentrate of 24% copper. With isopropyl and isoamyl xanthates, the recovery was improved but the grade was lowered. By conditioning the pulp with air-CO2 or oxygen-CO2 mixture, the recovery was lowered with ethyl xanthate only, mainly due to the depressant action of bicarbonate formed. Flotation with dixanthogens gave cleaner concentrates of chalcopyrite. because iron pyrite did not float with these collectors. Of the dixanthogens tried, diisopropyl dixanthogen gave the highest recovery, 99% chalcopyrite with a concentrate containing 28.5 to 30% copper, when the pulp at pH 8.5 was condi-tioned with air. Isopropyl dixanthogen was found to be the best collector of all the xanthates and dixanthogens studied. It was found that the adsorbed ethyl, isopropyl and isoamyl xanthates at chalcopyrite surface, activated by cupric sulfate, and at iron pyrite surface were oxidized to the corresponding dixanthogens to different degrees in presence of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture.' The dixanthogen formed at chalcopyrite surface was, however, firmly adsorbed while that at iron pyrite surface was easily desorbed. Since dixanthogens formed have greater hydrophobicity than the corresponding xanthates, as revealed by contact angles,1,2 the former were expected to improve the flotation results. It was, therefore, thought desirable to find out the effect of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture on the selective flotation of chalcopyrite when individual xanthates were used as collectors. The effect of direct use of dixanthogens as collectors on the selective flotation of chalcopyrite was also investigated. For these studies, low grade chalcopyrite ore, received from the Indian Copper Corp., Ltd. (I.C.C.), Ghatsila, Bihar, was employed. At the milling plant of the I.C.C., chalcopyrite is floated at a pH of 8.5, employing ethyl xanthate as collector. EXPERIMENTAL Materials Employed: XANTHATES - Ethyl, isopropyl and isoamyl xanthates of potassium were prepared in a pure state by the methods described earlier.4 A 0.03% aqueous solution of a xanthate was freshly prepared in air-free distilled water for flotation studies. DIXANTHOGENS - Diethyl, diisopropyl and diisoamyl dixanthogens were prepared by the oxidation of xanthates by iodine and purified by extraction with petroleum ether. A 0.03% alcoholic solution of dixanthogen was used as a collector. FROTHER - A 0.2% solution of pine oil in ethyl alcohol was employed. SODIUM CARBONATE - A 0.4 N solution was used. ORE - The composition of the -100 +200-mesh size (Tyler standard) powdered ore, as determined by standard methods of analysis, was: copper 1.57%, iron 10.29%, sulfur 3.15% and acid insolubles 66.10%. Iron present as chalcopyrite (CuFeS2) was 1.38%, while that present as iron pyrite (FeS,) was 1.37%. Both chalcopyrite and iron pyrite were found to be liberated from the gangue minerals and from each other, as observed under a microscope. Flotation of Chalcopyrite with Xanthates in Presence of Different Gaseous Systems: Fifteen grams of -100 + 200-mesh size ore were shaken well with 100 ml of distilled water. The pH of the pulp was adjusted to 8.5 by the addition of sodium carbonate solution. Then 0.1 ml of xanthate solution (0.005 lb xanthate per ton of the ore) was mixed with the pulp, and the latter together with washings transferred to a

Jan 1, 1963

By F. W. Jessen, James N. Howell

The accumulation of paraffin deposits in tubular goods has been recognized as a major production problem since the inception of the petroleum industry. This problem is not limited to any particular geographical area nor is it limited to a specific type of crude oil.' Generally speaking, "paraffin" deposition pertains to the deposition of any predominately organic material in flow lines, and possibly even at the sand face, which would hamper the production of oil. In some fields, a continuous effort is required to remove deposits of paraffin and in order to accomplish this, many unique methods have been devised. The best solution to this problem, however, is to prevent the formation of such deposits. One method which has been tried in a number of fields is the use of plastic pipe. The purpose of this investigation is to compare the relative effectiveness of several plastic materials to aid in the reduction or prevention of paraffin accumulations in surface flow lines. COMPOSITlON OF PARAFFIN DEPOSITS By definition, paraffin deposits are those materials which are insoluble in crude oil at the prevailing producing conditions of temperature and pressure. Such deposits1 s usually consist of small particles of petroleum wax intermixed with resins, asphaltic material, and crude oil. They may also contain a variety of foreign materials such as sand, silt, water, various metal oxides, sulfates and carbonates of iron. barium, and calcium. The petroleum waxes deposited in flow strings usually consist of both a "hard" and a "soft" wax fraction. These waxes are largely aliphatic hydrocarbons with smaller amounts of aromatic and naphthenic compounds. Nathan' has classified the hard and soft wax fractions. The aliphatic hydrocarbons present are those of high molecular weight with high melting points. Reistle3 pointed out that these high molecular weight compounds first separate from the oil due to a sharp decrease in solubility as the melting point increases. The identification of the resins and asphaltic materials rests, at present, on an arbitrary solubility procedure. Under certain conditions, materials which are insoluble in pentane (ASTM D-893) are defined as resins and asphalts. Subgrouping of these materials is made on decreasing solubility in benzene and carbon disul-fide. Shock' found some correlation be-tween the solvent response and the pentane insoluble content of paraftins: higher pentane insoluble fractions are less soluble in any of the commonly used commercial solvents. PARAFFIN CONTROL METHODS The methods used in oil fields to prevent and remove paraffin accumulations can be grouped into four general classes: (1) operative methods, (2) physical methods, (3) chemical methods, and (4) combination of any of these. Operative methods attempt to prevent the formation of paraffin deposits while the other methods are concerned primarily with the removal of these deposits. Plastic coated pipe has been used for a number of years to prevent cor- rosion in wells, and in manv instances paraffin deposits have -been greatly reduced. Field observations have indicated that plastic coated pipe not only reduced paraffin accumulation but in some cases eliminated deposition completely; however, data are needed to demonstrate the relative effectiveness of plastic materials. Deposition Apparatus The pipe used to determine the effect of velocity on rates of deposition was %- and 2-in. nominal diameter, and 5 ft in length. Steel, butyrate, rigid PVC, kralastic resin-type plastic pipes, epoxy coated pipe, PVC lined glass fiber pipe, and aluminum pipe were tested. Steel pipe was used as a control. Fig. 1 is a schematic diagram of the apparatus showing the relative position of the separate units making up the equipment. In order to facilitate the installation and removal of the test pipes in the apparatus, O-ring seals capable of sustaining pressures of 50 psi were provided at each end. Test pipes were submerged in a cold water bath maintained at or below room temperature by circulating water through copper cooling coils packed in ice. A hot water bath equipped with immersion-type heaters, stirrers, and a thermoregulator was used to maintain the temperature of the oil prior to introduction into the piping manifold. The capacity of the oil reservoir was 30 gal. A 33-gal/min centrifugal pump, capable of producing turbulent flow velocities in the test pipes, was used to circulate the oil through the system when using %-in. pipe; and a 70-galjmin centrifugal pump was used in later tests using 2-in. pipe. A by-pass arrangement made it pos-

By M. J. Duggin

Structural similarities between the E, X, and iron carbides are illustrated. Experimental evidence regarding phase transformations occurring during ternpering reactions in finely divided carbides, thin-film carbides, and carbides which occur in steels is considered and possible mechanisms for the E — x and x — 9 transformations proposed. HOFER1 has shown that within the appropriate temperature ranges carbon monoxide will react with finely divided a iron to form either iron carbide or x iron carbide. He has shown that at an elevated temperature the E iron carbide will transform to the x iron carbide (Hagg carbide) which, upon further elevation of temperature, will transform to 9 iron carbide (cementite). Jack,2,3 using X-ray diffraction methods, has observed that during the tempering reactions occurring in steel the E iron carbide formed in the first stage of tempering passes into two-dimensional platelets of 0 iron carbide during the second stage of tempering. The three-dimensional form of the 0 carbide is formed during the third stage of tempering. Jack suggested2 that the two-dimensional platelets of 0 carbide could be related to the faulted x iron carbide. Okada and Arata4 investigated a Swedish steel containing 1.05 wt pct C and approximately 1.0 wt pct Mn using permeability measurements at low field strength. A Curie point of 360°C was observed in the quenched steel, which indicated the presence of E iron carbide. On tempering at 400°C the specimen developed a Curie point at 230°C, indicating the presence of x iron carbide, and on tempering at 700°C the specimen developed a Curie point at 190°C which was assigned to 0 iron carbide. The carbides were extracted electro-lytically and the use of X-ray diffraction techniques4r5 indicated the carbide with a Curie point of 230°C to be x iron carbide. The Curie points of the carbides are 10 to 22°C lower than the accepted values which is probably due to the presence of manganese in the carbides, since it has often been observed (e.g., Ref, 6) that a partial substitution of manganese for iron in cementite will lower the Curie point of this carbide. Hofer' summarizes additional evidence of the tempering reactions in steel in which E iron carbide, formed during the first stage of tempering, transforms to x iron carbide during the second stage of tempering. During the third stage of tempering, the x carbide disappears as the 0 carbide is formed. By carburizing thin iron films in a CO gas stream, ~a~akura' has been able to produce the E, X, and 0 iron carbides. He found that below 250°C the E iron carbide was formed; between 250" and 350°C the x iron carbide was formed and above 350°C the 0 iron carbide was formed. He has shown that the E iron carbide transforms to form x iron carbide at 380" to 400°C and that the x ir°n carbide transforms to form the 0 iron carbide at approximately 550" C; both of these phase transformations are irreversible. Hofer' presents a review of evidence to show that the sequence of reactions occurring during tempering processes subsequent to the formation of E iron carbide formed by the direct carburization of finely divided a iron is the same as the sequence of reactions which occur during the tempering processes subsequent to the formation of E iron carbide in steel during the first stage of tempering. It is evident from Nagakura's work that identical tempering reactions are found in thin films of iron which have been carburized to form iron carbide. The purpose of this paper is to discuss the structural similarities between the E, X, and 0 carbides and to suggest a possible mechanism by which regions of the E carbide, formed during the first stage of tempering, may transform to the x carbide during the second stage of tempering. For the finely divided or thin film carbides a mechanism will be proposed for the transformation of the x carbide to the 0 carbide during the third stage of tempering, although it will be suggested that there is evidence that such a transformation may not occur in steels. STRUCTURAL DATA OF THE E, X, AND 0 IRON CARBIDES € Iron Carbide. It is evident from X-ray diffractions and electron diffraction', investigations that the metal atoms in the E iron carbide form an hcp structure with lattice constants ah = 2.752A, ch = 4.3534, using electron diffraction, reports the lattice paramet$rs of the superlattice cell to be a = 4.767A, c = 4.354, c/a = 0.9134. He finds that the carbon atoms occupy the octahedral voids in the metal atom structure so as to form a hexagonal stacking sequence with its basal plane parallel to that of the metal atoms. Considerable long-range disorder occurs in the positioning of the carbon atoms, however, which is in agreement with the possible range of composition Fe2C-Fe3C discussed by Hofer.' Barton and ale" have made X-ray diffraction measurements on a sample of E iron carbide extracted from a catalyst in an organic process. Although there were few reflections recorded on the obtained X-ray powder diffraction pattern, they have proposed that the structure could belong to one of the three possible space groups p3m1, P63/mmc, or Pbcn if one assumed the composition to be Fe2C. Nagakura, using electron diffraction data, suggests a space group of P 6322 for a specimen of c iron carbide of apparent composition Fez.&. x Iron Carbide. The x iron carbide has been studied by Duggin and Hofer" and by Jack and wild,' who

Jan 1, 1969

By D. E. Hawk, R. F. Burdyn, F. D. Patchen

Earlier work on a mud separator for barite recovery is extended to the design and construct ion of a rugged field unit. Problems associated with scale-up for field use include the me of dilution water and its effect on capacity, power requirements and pressures developed. Equations for these quantities are derived and applied in maximizing the beneficial effects of dilution and minimizing the power required. Tests on the full-size rotor show that its performance can be predicted by theory. The completed unit is compact and lighter than current decanting types. Its capacity is from 10 to 22 gal/min with corresponding barite recovery efficiencies of 92 to 86 per cent. INTRODUC'TION In an earlier publication a new type of centrifugal device was described for solid-liquid separations.l In that paper an operating equation was derived, and its validity demonstrated in laboratory scale experimentation. Some of the features apparent in this new device seem particularly well suited to the conservation of barite in field drilling-mud systems, hence the development was extended to the design and construction of a field unit. In the present paper the design problems associated with scale-up are considered. A full-scale, rugged self-contained field unit is described, and test results discussed which verify that the performance of the large field unit can be described by a simple operating equation. PRINCIPLE OF OPERATION OF SEPARATOR In principle, the new device is simply a perforated cylinder rotating within a body of fluid which is contained within a stationary case, as in Fig. 1. The frictional drag generated by the rotating cylinder causes part of the fluid to rotate. At the surface of the cylinder, assuming no slip occurs, the angular velocity of fluid and of the cylinder are identical. If there are suspended particles present of greater density than the fluid, the centrifugal force acting on these particles causes them to move radially away from the cylinder at some velocity vp . Where the Stokes settling equation holds, this velocity may be expressed as:2 d2 ?p rw2 If the case is provided with openings at both ends, a suspension can be pumped in at one end at a fixed rate. Part of the suspension can then be removed at a fixed rate at the other end of the case as underflow, and the remainder forced through the perforations and hollow shaft of the rotor to appear as effluent, also at a fixed rate. The radial component of the flow velocity of this stream as it reaches the rotor surface, is simply effluent flow rate divided by cylindrical surface area: Because up is a function of particle size, for some particular particle size, the velocities vp and v, will be equal in magnitude. This is defined as the critical particle size and represents the size above which all particles appear in the underflow and below which all particles appear in the effluent. For this equilibrium condition at the rotor surface, Eqs. 1 and 2 combined give

Jan 1, 1966

By Kenelm C. Appleyard

In introducing to an American audience a description of the work done in dry coal separation in England and in Europe generally, it is perhaps desirable to give a short history of the development outside the United States of the particular processes with which the author is connected, and perhaps to stress a little the differences in the nature of the conditions to be faced. England actually presents one set of problems and the Continent of Europe another, since the character of the coals to be treated is entirely dissimilar, and the attitude of the coal industries towards coal preparation is also dissimilar. England for generations has been working by hand good seams of clean coal of the highest possible quality and has not felt any pressing need to clean its coal. Most Continental countries, however, especially in Central and Western Europe, have been working friable and often very dirty coals for so long that a washery is accepted as a part of the normal equipment of a colliery, with the result that the art of wet washing has reached a high state of perfection, particularly in Belgium and Germany. The advent of machine mining has intensified the problems to be faced in all countries, and in England has been coupled with the working out of the best seams in the older coal fields, thus bringing about the necessity of working thinner and dirtier seams with resultant difficulties as regards marketing the products, while Poland, with clean and well prepared coal, has in recent years been attacking established British markets in Scandinavia. In recent years, therefore, interest in coal preparation has been steadily gaining ground in England, although it has not yet reached Continental dimensions. Broadly speaking, the differences in preparation problems between England and the Continent boil themselves down to one of size. In England, for example, with the exception of the Kent coal field, the proportion of coal of a size less than ? in. to the coal less than 2 in. is very much less than on the Continent, and since the principal difficulties in dry cleaning lie in the fines it is easier to produce good figures on

Jan 1, 1931

By Gustav Egloff

AN unexpected and unprecedented demand for its products now challenges the petroleum industry. Between 1939 wand 1946, domestic oil demand increased nearly 45 per cent and in the first half of 1947 it was 10 per cent higher than in 1946. In 1939 the United States produced 1,264,962. 000 bbl of crude oil and indications are that about 1,860,000,000 bbl will be produced in 1947, a 47 per cent increase. Runs to stills are more than keeping pace with production. The crude capacity of 365 operating refineries is rated as 5,400.000 bbl daily and almost 100 per cent of this capacity was running crude oil in August 1947. The oil industry is cognizant of our need for a greater volume of petroleum products and is expending the huge stun of four billion dollars on exploration. production. transportation, refining. and marketing of petroleum. Of this amount about half will be spent on exploration and production. a billion on refining. and another billion on transportation and marketing facilities.

Jan 1, 1947

By John R. Don

This paper, under the title of "The Genesis of Auriferous Lodes from a Chemical Point of View, Illustrated by Analyses of Samples Taken from the Chief Auriferous Area of New Zealand, Victoria and Queensland, by John R. Don, D.Sc., M.A., Lecturer on Geology in the University of Otago, N. Z.," was submitted by the author with the frank confession that its length, covering several hundred printed pages of the Transactions of the Institute, would preclude its acceptance for publication in full. But the great value of the original work which it records rendered its rejection on that ground highly undesirable ; and, after correspondence with Dr. Don, it was agreed that the Secretary should condense the paper, subject to the author's approval, omitting what was not essentially connected with the original work reported. In the discharge of this laborious and difficult duty, the Secretary's chief trouble has been his regret to cut out the acute criticisms and admirable theoretical and historical summaries of Dr. Don on the general subject of the science of ore-deposits. It should be added, that the original paper has been returned to the author, with full permission to publish it through any other medium (due mention being made of the first publication by the Institute of portions thereof), and a cordial expression of the hope that the treatise, as a whole, may be thus published, to the advantage of science. The Secretary begs to add, that many of the portions necessarily omitted from this condensed version would constitute, in his judgment, interesting and valuable separate contributions. In attempting to condense this paper, it was necessary at the outset to cut out the tint three chapters, of which the following brief outline is therefore given. Chapter I., introductory in character, indicates the importance of chemical analysis in the investigation of the genesis of ore-deposits, emphasizing the value of Prof. Posepny's Institute paper, and especially of the discussion which it aroused, and stating in general terms the theories of "lateral secretion" and "ascension." Chapter 11. describes the scope of the investigation undertaken by the author, the chief purpose of which was to determine which of the above-named theories was favored by the evidence obtained. This evidence consists chiefly (though not wholly) of analyses of the country-rock taken at various distances from the auriferous "reefs," (a) on deep mine-levels; (b) in the surface or "vadose" region : and also (c) of underlying, neighboring or connected crystallines (granite, gneiss, etc.). In addition to these investigations, there is a separate inquiry into the question of the deposition of gold in marine basins, suggested by the fact that most of the gold in the lodes of Australasia occurs in stratified deposits. Chapter 111. discusses the principles and methods followed by the author in the examination of country-rock for the purpose described. After giving his reasons for believing that careful tests of carefully-chosen samples of country-rock taken at varying distances from the ore-deposit might throw light upon the question

Jan 1, 1898

By John J. Gilman

BECAUSE of their layerlike structure, zinc crystals exhibit strong anisotropies for almost all physical and chemical properties. This should, and indeed does, greatly influence the plasticity of zinc for various crystal orientations. At low temperatures, the investigator of this plastic anisotropy is plagued by the great variety of deformation modes that operate. However, at high temperatures (250° to 419°C) only two deformation modes predominate: basal (0001) and prismatic (1010) glide. Furthermore, since strain hardening is virtually absent at high temperatures, the plasticity for these two modes of deformation can be very simply described by means of two equations of state. It is the purpose of this paper to describe the experimental behavior of basal and prismatic glide in zinc crystals, and to interpret this behavior in terms of other physical properties (in particular, the thermal expansion coefficients and the elastic constants) using the theory of dislocations. Fig. 1 defines the two planes of the zinc structure that will be discussed. Glide occurs very readily on the basal planes at all temperatures, and there is a very large literature on this subject. Much of the literature has been reviewed by Schmid and Boas;' it will not be reviewed here. Kolesnikovl was the first to show that if basal glide is circumvented by stressing a zinc crystal parallel to the basal planes (giving zero shear-stress on the basal planes) then, at temperatures above about 320°C, glide on the first-order prism planes occurs. His results have recently been confirmed by Cahn, Bear, and Bell." These previous workers have established the existence and crystallographic elements of prismatic glide; the present paper is concerned with the stress, strain rate, and temperature relations of prismatic glide as contrasted with basal glide. Experimental Methods The crystals were square ones, 6x6 mm, that had been grown in precision Pyrex tubes by a method that is described in detail elsewhere.' Most of the crystals were 99.999+ pct Zn (New Jersey Zinc Co. CP grade). Some were alloyed with 0.1 -+-0.005 atomic pct Cd, and chemical analysis showed that almost all of the added cadmium persisted through the crystal-growing process. For measurements of nonbasal glide, crystals were oriented with their basal planes parallel to both the rod axis and one of the flat faces of the square cross section. However, the orientation of the close-packed directions [1210] with respect to the rod-axis was variable. For basal glide measurements, the angle between the basal plane and the specimen axis was 35". The orientations were measured by the Gren-inger back-reflection X-ray method. The problem of finding a suitable method of gripping the crystals was the most serious experimental obstacle that arose. Because of the large plastic anisotropy of zinc, the usual gripping methods were unsatisfactory. Some methods that were tried were: high melting-point solder, making heads on the ends by locally melting a crystal, and electroplating nickel on the ends to form enlarged portions. For all these methods, the regions of the grips were weaker than the crystals themselves. Finally, two methods were decided upon: bend tests and direct machining of tensile specimens. In the bend tests, specimens were loaded as simple beams so that gripping was not a problem. The beams were 1 in. long and the axis of bending was parallel to the hexagonal axis of the crystals. For the crystals that were machined into tensile specimens, brass bars with slots in them were used to support the crystals, and thereby minimize the distortions due to machining. The crystals were glued into the brass bars with plastic cement which was later dissolved away with acetone. See Fig. 2, left. No clamps were used near the crystals and the machining was done using a milling machine with a fly-cutter. The tool bit was very sharply pointed to minimize burnishing. The feed was less than 1 mil per cut. The depth of cut was 2 mil for roughing cuts, and % mil for the finishing cuts. This machining method produced surface layers of tiny recrys-tallized grains only 2 to 3 mil deep, and the bodies of the crystals were not measurably disturbed. After the crystals had been machined and removed from the brass holders, they were chemically polished until about 5 mil had been removed from all their surfaces. The polishing reagent consisted of equal parts of concentrated HNO,, 30 pct H3O and ethyl alcohol; it is described in detail elsewhere." A typical crystal is shown in Fig. 2, right. The I-shaped faces are normal to the hexagonal axis of the crystal; otherwise the projections at the ends would simply shear off when the crystal was loaded. The cross section in the 2?-in. gage length is 0.215x0.115 in. It was found that the polished

Jan 1, 1957

By W. W. Duecker

SULPHUR is a peculiar combination of a nuisance and a useful element. Most of the nonferrous metallic ores contain large amounts of it in the form of sulphides, which the metallurgist has wasted up the chimney, since the sulphur dioxide formed is generally too dilute to make recovery economical and practical. Iron ore does not contain much of the unwanted sulphur; in pig iron and coke it is most unwelcome. Gold metallurgists can get along nicely without sulphides in their cyanide plants and yet they find matte-a sulphur compound -an excellent collector for gold and silver in base-metal smelting. Also, sulphur appears in the non-metallics as in barite, gypsum, Glauber's salt, and celestite, all to useful purpose.

Jan 1, 1938

By Thunaes, Arvid

Pilot plant test work in 1942 and 1943 showed that by a combination of desliming, fine-size classification, and Sullivan deck concentration it is possible to recover heavy minerals such as cassiterite at least as fine as 10 microns in size. This appreciable improvement in gravity concentration practice has been substantiated by several full-sized plants.

Jan 1, 1950

By Å. Sterten, R. Tunold, J. Brun, K. Dalatun

c axis compression behavior of beryllium single crystals at three purity levels under hydrostatic pressures up to 27 kbars was determined. Extensive non-basal slip, observed by two-surface trace analysis and transmission electron microscopy, occurred under a hydrostatic pressure of about 12 kbars (175 ksi) for the high-purity (twelve-zone pass) material and at about 19 kbar (275 ksi) for the lower-purity (zone-leveled) material. Prismatic loops with a (c + a) Burgers vector were observed in association with second-phase parti- A principal factor limiting the use of beryllium is its brittle behavior when tested at the usual strain rates (E = 10-4 sec- 1) at temperatures below about 200°C and under impact conditions at temperatures in excess of 200°C. It has been proposed' that the brittle-ness of beryllium is associated with the lack of a sufficient number of independent slip modes and the absence of a slip mode with a Burgers vector out of the basal plane [presumably (c + a) pyramidal slip mode] and to the ease with which beryllium cleaves on the basal and second-order prism planes. The absence of pyramidal slip has been attributed to a high Peierls-Nabarro stress associated with the motion of dislocations with a (c + a) vector and the ease with which cleavage occurs on the basal and second-order prism planes. The experimental evidence in support of the proposed explanation for the brittleness of beryllium is far from complete; for example, that the ductile-to-brittle transition in polycrystalline beryllium is associated with the operation of profuse (C + a) slip has not been unequivocally established. The occurrence of (c + a) slip ({1122}(1123)) has been experimentally established2-5 under conditions where basal and prism cleavage are restricted in a c axis compression test. In these investigations (C +a) slip was found in high-purity beryllium single crystals tested in c axis compression* at 200°C and in Be-4.4 pct Cu and Be-5.2 pct cles in the lower-purity materials tested. The loops were related to surface "extrusions" observed on many of these same specimens. Nonbasal dislocations operating on (1122) planes with a (c + a) Burgers vector were observed. The presence of c and a dislocations together with (c + a) dislocations suggests that the (c + a) dislocations dissociate presumably on unloading or after failure of the test crystals to c and a dislocations. terial, (c + a) slip has only been observed near the the fracture4 surface in room-temperature c axis compression tests. Fracture in these tests occurs without measurable plastic flow, as determined with a strain sensitivity of 10"6. Since it has been shown for many metals that the application of hydrostatic pressure suppresses fracture,?-' it was felt that studying the behavior of unalloyed beryllium single crystals stressed in c axis compression under a hydrostatic pressure would reveal whether (c + a) can occur if fracture was prevented, and that it might elucidate the role of (c + a) slip in the ductile to brittle transition. Evidence that (C + a) slip is associated with increased ductility in a high-pressure environment has been found in stress-strain tests on poly crystalline beryllium.10 The present paper describes a study on the influence of a hydrostatic pressure environment on the occurrence of (c + a) slip in beryllium single crystals. Material of two purity levels was tested in c axis compression over the pressure range ambient to about 27.5 kbars.* 1) MATERIAL PREPARATION AND CHARACTERIZATION Two lots of low-purity single-crystal beryllium were used. The first lot was "ingot secondary refined grade" and designated lot A. The second lot (lot B) was produced by a two floating zone pass zone-leveling operation in an argon-filled sealed quartz apparatus on a 1-in.-diam by 12-in.-long bar of Pechiney secondary refined-grade vacuum-cast and hot-extruded material. The high-purity material (lot C) was made by traversing twelve floating zone passes through a similar bar of Pechiney secondary refined-grade vacuum-cast and hot-extruded material. In a series of spark cutting and lapping procedures,11 single-. crystal specimens some 0.12 in. sq by 0.30 in. high were made with the sides Parallel to the first- and second-order prism planes and the basal plane within 3' of arc of the top and bottom surfaces of the specimen. Such an accurate orientation is necessary because of the large difference in resolved shear stress

Jan 1, 1970

By Guillermo Zuloaga

The iron deposits of the Imataca Range of Venezuela, which occur along the Orinoco River, in the northern border of the Guayana Highlands, have lately attracted attention on account of their economic possibilities. Many deposits occur in this area; some of slight economic importance and others that may rank with the largest masses of high-grade iron ore of the world. The geology and the character of the ores seem to be remarkably similar to those of the large iron deposits of Brazil. In the investigation of the Venezuelan deposits a definite relationship has been found between the mineralization of the large orebodies and igneous intrusions, especially norites and granites. The following paper is the result of a field and laboratory investigation of the ore deposits. The field work was done during the months of February and March of the year 1929, partly in the company of Prof. W. H. Newhouse. The laboratory studies have been made in the Massachusetts Institute of Technology, under the supervision of Professor Lindgren and Professor Newhouse. GENERAL GEOLOGY OF GUAYANA HIGHLANDS General Geography and Physiography The Sierra de Imataca proper occupies a narrow belt along the south bank of the Orinoco River, in the northeastern part of the State of Bolivar and in the western part of the Delta Amacuro Territory of Venezuela. The State of Bolivar is generally known as the Venezuelan Guayana, as it forms part of the same physiographic province of the Guianas and northeast Brazil. In general the Venezuelan Guayana is an extensive plateau, sloping gently towards the Orinoco River to the north and towards the Atlantic Ocean to the east. In the northern part mountains are rare, and consist mainly of elongated low hills. Towards the British Guiana-Brazil boundary, table mountains with vertical cliffs are found forming the ranges of Parima, Roraima and Pacaraima. General Geology The Guayana Highlands are the northern extension of the Brazilian Archean shield. Only a few scattered masses of sediments remain on its

Jan 1, 1935

By H. A. Lesser, H. L. Stone, G. H. Bruce

ESSO PRODUCTION RESEARCH CO., HOUSTON, TEX. A mathematical model that represents the conduction heating of a rock formation of limited permeability is formulated. Heat is introduced by the injection of a hot condensing gas into horizontal fractures through the formation. The fractures are assumed to be equally spaced; the flow of fluid is linear. The model consists of three coupled partial differential equations and two functional relationships. Temperature histories for both fractures and formation are obtained by numerical procedures. Application of the model in predicting in situ heating of oil shale is illustrated with four sample cases. Influences of shale thermal diffusivity, fluid pressure in the fracture and fracture spacing upon heating rate are demonstrated. In all cases considered, several years were required to heat all the formation to 700F with 1,000F steam. Less than 32 per cent of the injected heat was utilized for heating the shale. To facilitate extensive calculations of this type, a set of seven dimension-less quantities are derived. With this dimensionless system, the effect of controllable parameters on economics can be explored. INTRODUCTION Vast deposits of hydrocarbons are contained in oil shale formations in the western United States and in other countries. These hydrocarbons, known as kerogen, are difficult to recover because they are immobile solids and because the rock formations in which they are found have very limited permeability. The kerogen can be converted through pyrolysis to recoverable liquids and gases if the formation temperature is elevated to the range 600 to 800F. To accomplish this heating, the formation might be artificially fractured and a hot fluid injected into the fractures. If the injection and production wells are vertical and the fractures horizontal, interwell communication will be established and the hot fluid will flow from an injection well to a production well. In this process, some of the heat in the fluid will be given up and conducted into the formation. Products of pyrolysis will flow from the heated rock matrix into the fractures and be produced, commingled with the injected fluid. The practicality of such a process is strongly influenced by the rate at which heat can be transferred from the hot fluids to the formation. An analysis of this heat conduction problem is the subject of this paper. Linear flow of a condensing gas through a set of horizontal, equally spaced fractures is considered. Temperature histories for both fractures and formation are obtained from numerical procedures. The analysis also applies to formations containing streaks of natural permeability instead of fractures. Heat flow problems similar to the one treated here have been studied by other workers. Thomas1 has solved a radial problem in which he considers the injection of a noncondensing gas into a single, horizontal fracture and approximates the temperature profile in the fracture by a step function. The solutions to other problems, which are less similar to the present problem than the one treated by Thomas, have been reviewed by Spillette.2 In addition to these mathematical studies, a field test of an in situ shale oil recovery process using hot natural gas as the injected fluid has been reported.3 The first part of this paper is concerned with the mathematical development of the problem. The differential equations, boundary conditions and functional relationships which describe the physical model are formulated and the equations are cast into finite difference form. The method of solution of the difference equations is discussed (Appendix B). The second part of this paper presents results computed for a typical oil shale formation for which steam at 1,000F is the injected fluid. Fracture spacing, horizontal and vertical thermal diffusivities

Jan 1, 1967

By W. E. Hale, G. J. S. Govett

An orientation survey was conducted over a known disseminated copper deposit and a Au-Cu vein deposit and employed geological, geophysical, and geochemical methods. Geochemical techniques proved the most effective and economical means of locating and defining areas underlain by these types of mineralization. Six additional, widely separated occurrences were also investigated and mineralization was confirmed by determination of cold-extractable copper in stream sediments. The length of anomalous drainage varies from several to 16 km and depends on the type and tenor of mineralization. Despite generally marked relief and extreme physical and chemical weathering, cold-extractable copper anomalies in soils appear to reflect closely variations in the ore mineral content of immediately underlying rocks. Threshold values vary with local geological conditions and type and grade of mineralization. Significant thresholds in stream sediments are about 65 ppm and 10 ppm for cold-extractable copper in disseminated and vein copper occurrences respectively. Similar differences are encountered in soils. This necessitates the use of a scale of threshold values at progressive stages in each exploration program. Dis-seminated copper occurrences are presently the major source of mineral production m the Philippines. Much potentially productive ground remains to be investigated and applied geochemistry appears to offer the best available approach. The Institute of Applied Geology (I.A.G.), a joint project sponsored by the University of the Philippines, the Philippine Bureau of Mines and the United Nations Development Program (Special Fund) undertook during 1965-66 a number of field projects in Northern Luzon Island (Fig. 1). These field operations were of a two-fold nature and involved both orientation and exploration. During approximately six weeks, an orientation survey, involving geological mapping, geophysical surveying and geochemical prospecting, was conducted over a partly developed, disseminated copper deposit at Santo Nino (Fig. 1). This study demonstrated the economic and technical feasibility of geochemical ptospecting, relative to the other methods tested, for the location and delineation of a typical disseminated copper occurrence characteristic of those that represent the major source of metal in the Philippines.' Geochemical techniques, similar to those tested at Santo Nino, were then applied in a second orientation study of a vein occurrence at Suyoc (Fig. 1). The results of these two orientation studies suggest that, in reconnaissance work in this region, stream sediment analyses, combined with the determination of pH in the same streams, can be used to indicate areas underlain by rock containing anomalous concentrations of copper, whether it occurs in the large tonnage, low grade, disseminated deposits or in the comparatively small tonnage, higher grade, gold vein occurrences. Furthermore, the orientation surveys demonstrate that soil sampling and analysis serve effectively to outline more closely the mineralized zones within the generally anomalous areas identified from the stream reconnaissance. To further test the methods selected from the two earlier trials, six additional, widely separated prospects were investigated. The geological and geochem-

Jan 1, 1970

By G. F. Bolling

Single crystals of each metal were deformed at 77°K and heated at constant rates, variously in the range 0.125" to 4o°Kper min from 77" to -390oK, while being monitored in an X-ray diffractometer. Changes in diffraction-peak heights and line breadths were used to ascertain the temperature ranges of recrystalliza-tion. The results were subjected to the analysis of nicholas' in order to obtain the rate-controlling activation energies,Q. In this analysis no recourse to a separate and distinct nucleation stage is required and the results of studying recrystallization proved consistent with the hypothesis of a constant number of nuclei or equivalent hypotheses. The values Pb = 5.5 ± 0.5 keal per mole Zn ~ 7.5 Sn - 5 Bi - 9. 5 correspond for lead, zinc, and tin to activation energies obtained elsewhere for grain boundary migration, and for bismuth and lead to previous studies of re-crystallization by Barrett.6 This correlation allows the conclusions that interference from recovery was minimal and that the observed recrystallization rates in these pure metals are effectively governed by grain boundary migration. Good agreement was not found between the results of this kind of study in zone-refined aluminum and previous work; and supplementary isothermral experiments involving hardness tests and metallography did not resolve the discrepancy. Nevertheless, at least a range,Q = 11.5 ± 2 keal per mole, can be assigned to the activation energy for boundary migration in aluminum. An experimental study of one aspect of the recrystallization process is presented here for four metals of different crystal structure. The metals chosen for study were all zone-refined to reduce impurity effects, but the attendant high purity presented a difficulty. For any reasonably high driving force a "re-crystallization temperature", TR, is in the range of 0.25 T,, where T, is the absolute melting point, and study was therefore restricted to lower temperatures. An X-ray technique under constant heating-rate conditions adequate above 90°K was devised for the study; in consequence, a newer type of analysis following Nicholas1 had to be used to obtain quantitative information about activation energies. The standard methods of studying recrystallization have involved the comparable analyses of Johnson and Mehl2 and Avrami3 which are reviewed by Burke and Turnbull.* The general analysis4 which is applied only to isothermal studies using any of various investigative techniques states:

Jan 1, 1968

By Guillermo Zuloaga

The iron deposits of the Imataca Range of Venezuela, which occur along the Orinoco River, in the northern border of the Guayana Highlands, have lately attracted attention on account of their economic possibilities. Many deposits occur in this area; some of slight economic importance and others that may rank with the largest masses of high-grade iron ore of the world. The geology and the character of the ores seem to be remarkably similar to those of the large iron deposits of Brazil. In the investigation of the Venezuelan deposits a definite relationship has been found between the mineralization of the large orebodies and igneous intrusions, especially norites and granites. The following paper is the result of a field and laboratory investigation of the ore deposits. The field work was done during the months of February and March of the year 1929, partly in the company of Prof. W. H. Newhouse. The laboratory studies have been made in the Massachusetts Institute of Technology, under the supervision of Professor Lindgren and Professor Newhouse. GENERAL GEOLOGY OF GUAYANA HIGHLANDS General Geography and Physiography The Sierra de Imataca proper occupies a narrow belt along the south bank of the Orinoco River, in the northeastern part of the State of Bolivar and in the western part of the Delta Amacuro Territory of Venezuela. The State of Bolivar is generally known as the Venezuelan Guayana, as it forms part of the same physiographic province of the Guianas and northeast Brazil. In general the Venezuelan Guayana is an extensive plateau, sloping gently towards the Orinoco River to the north and towards the Atlantic Ocean to the east. In the northern part mountains are rare, and consist mainly of elongated low hills. Towards the British Guiana-Brazil boundary, table mountains with vertical cliffs are found forming the ranges of Parima, Roraima and Pacaraima. General Geology The Guayana Highlands are the northern extension of the Brazilian Archean shield. Only a few scattered masses of sediments remain on its

Jan 1, 1935

By M. Sheffield

This paper presents a technique lor predicting the flow of oil, gas and water through a petroleum reservoir. Gravitational, viscous arid capillary lorces are considered, and all fluids are considered to be slightly compressible. Some theoretical work concerning the fluid flow in one-, two- and three-space dimensions is given along with example performance predictions in one- and two-space dimensions. INTRODUCTION Since the introduction of high speed computing equipment, one of the goals of reservoir engineering research has been to develop more accurate methods of describing fluid movement through underground reservoirs. Various mathematical methods have been developed or used by reservoir engineers to predict reservoir performance, 193-5,7,8 The work reported in this paper extends previously published work on three-phase fluid flow (1) by including a rigorous treatment of capillary forces and (2) by showing certain theoretical mathematical results proving that these equations can be approximated by certain numerical techniques and that a unique solution exists. DISCUSSION The method of predicting three-phase compressible fluid flow. in a reservoir can be summarized briefly by the following steps. 1. The reservoir, or a section of a reservoir, is characterized by a series of mesh points with varying rock and fluid properties simulated at each mesh point. 2. Three partial differential equations are written to describe the movement at any point in the reservoir of each of the three compressible fluids. All forces influencing movement are considered in the equations. 3. At each mesh point, the partial differential equations are replaced by a system of analogous difference equations. 4. A numerical technique is used to solve the resulting system of difference equations. Capillary forces have been included in two-phase flow calculations.1,4,8 The literature, however, does not contain examples of prediction techniques for three-phase flow that include capillary forces. Where capillary forces are considered, each of the three partial differential equations previously discussed has a different dependent variable, namely pressure in one of the three fluid phases. Therefore, three difference equations must be solved at each point in the reservoir. Where large systems of equations must be solved simultaneously, an engineer might question whether a unique solution to this system of equations actually exists and, if so, what numerical techniques may be used to obtain a good approximation to the solution. It is shown in the Appendix that a unique solution to the three-phase flow problem, as formulated, always exists. It is also shown that several methods may be used to obtain a good approximation to the solution. The partial differential equations and differenceequations used are shown in the Appendix. Matrix notation has been used in developing the mathematical results. Two sample problems were solved on a CDC 1604. They illustrate the type of problems that can be solved using a three-phase prediction technique. SAMPLE ONE-DIMENSIONAL RESERVOIR PERFORMANCE PREDICTION A hypothetical reservoir was studied to provide an example of a one-dimensional problem that can be solved. Of the several techniques available, the direct method of solution as shown in the Appendix was used. The reservoir section studied was a truncated, wedge-shaped section, 2,400 ft long, with a 6' dip. (A schematic is shown in Fig. 1.) This section was represented by 49 mesh points, uniformly spaced at 50-ft intervals. The upper end of the wedge was 2 ft wide, and the lower end was 6 ft wide. The section

Jan 1, 1970

By A. J. Ardell, O. D. Sherby

The elevated-temperature steady-state creep behavior of polycrystalline a Zr was studied in vacuo under constant tensile stress. The experiments were conducted from 660° to 845°C over the stress range 870 to 5400 psi. The steady-state creep rate, is, of a Zr was found to be related to the applied stress, a, and temperature, T, by the equation where C is a constant. Two interpretations of the data are considered, each requiring different values of the parameters ß, Q, and . It is shown that this formula can be derived using Gilman's phenomeno logical equation relating dislocation velocity to the shear stress for the case where dislocation mobility is limited by the nucleation of kink motion. From the fundamental dependence of strain rate on dislocation velocity and the density of mobile dislocations, the factor exp(ßo) can be related to the stress dependence of the dislocation density, and Q to the energy of kink formation. The two interpretations considered are as follows: Case I—the parameters are adjusted so that the equation above describes the data over the entire range of stress and temperature, implying that creep is controlled exclusively by dislocation glide; Case IIthe parameters are adjusted to allow for the possibility that creep is diffusion-controlled at high stresses but glide-controlled at low stresses. For both cases the values of the parameters are within the spread permitted by the data. Factors favorable to the observation of the unusual stress -dependence of i, for a Zr are discussed and it is shown that the anomalously rapid rates of self-diffusion and the low modulus on the principal glide system are primarily responsible for the anomalous creep behavior. Metal-lograflhic observations are presented and discussed with reference to the overall creep behavior. PREVIOUS investigations of the creep behavior of a Zr have been conducted from room temperature to about 500C The results of these investigations are primarily of engineering significance because of the variety of conditions under which they were carried out, and the low testing temperatures employed. Little information is available concerning the fundamental nature of the elevated-temperature creep behavior of a Zr. This investigation of the creep behavior of a Zr above half the melting temperature (the melting temperature, T,, of a Zr is estimated to be about 1860"K was initiated because there are two significant anomalies of the physical properties of a Zr: a) the rate of self-diffusion in polycrystalline a Zr is anomalously rapid: b) both Young's modulus for polycrystalline a Zr and the shear modylus as-sociated with the prismatic slip system { 1010)( 1120) (the principal slip system in a Zr 7) have anomalously large temperature variations The importance of these quantities to the understanding of creep behavior has been demonstrated, and it was hoped that this investigation would provide a critical test of the predictions based upon the analysis of creep data for other pure metals. However, as the investigation progressed it became increasingly clear that the unusual creep behavior of a Zr could not be analyzed in a conventional manner. 1) EXPERIMENTAL EQUIPMENT AND PROCEDURES Two grades of zirconium, designated A and B, were used in this investigation. The analyses, as supplied by the vendors, are presented in Table I. Material A, with a nominal purity of 99.84 pct, was supplied by the Wah Chang Corp. in the form of cold-rolled sheet from which specimens were machined without further fabrication. Material B, with a nominal purity of 99.95 pct, was purchased from the Nuclear Materials and Equipment Corp. in the form of iodide crystal bar.

Jan 1, 1968

THE developments in construction and operation of the basic open-hearth furnace that have taken place in recent years have placed new emphasis on the vital influence played by regulation and control of the combustion system in both furnace production and furnace life. The several factors influencing flame development, such as regulation of fuel supply, air supply, air preheat, furnace draft, and furnace reversal, must be controlled closely if successful furnace performance is to be accomplished. Rugged instrumentation of distinctive design is required to sup- ply dependable information concerning operating conditions, which is requisite to proper regulation of combustion. This chapter attempts to give a practical discussion of the various features of open-hearth practice and instrumentation related to the efficient heating of the furnace, control of temperature, and protection of the furnace structure from accidental overheating. The appended references will be helpful to readers wanting a more detailed treatment of individual topics. OPEN-HEARTH FUELS The most important open-hearth fuels are listed in Table 4-1 together with their compositions and other data useful for combustion calculations. A detailed discussion of open-hearth fuels is not attempted here, but certain factors peculiar to their application to this type of process are briefly indicated on the following pages. Very often an open-hearth shop is forced by economic factors to use a fuel to which its furnaces are not very well adapted, because the general fuel-allocation scheme for the works as a whole seems to demand it. Often a variable marginal supply of coke-oven gas or tar must be consumed by the open hearth, together with another fuel such as producer gas, natural gas, or oil, to fill out total requirements. Most furnaces employ more than one kind of fuel during their useful life; however, the partial redesign

Jan 1, 1964